But Spain, featuring only five of the players that started their last-16 World Cup penalty shootout defeat by Russian Federation, hit back before halftime through Saul Niguez and Rodrigo.
Shaw left the field on a stretcher wearing an oxygen mask and a neck brace after lengthy treatment but was "up and talking" in the change rooms.
There were strong performances all around, but it has to be said that David De Gea came to La Roja's rescue late on.
Rodrigo then put Spain in the lead in the 32nd minute, cleverly redirecting an inswinging Thiago free kick at the near post to beat Jordan Pickford in the England goal.
England and Spain will also face World Cup runners-up Croatia in League A Group 4 of the UEFA's new tournament created to add spice to the global calendar.
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England teammates expressed relief about Shaw's injury, with manager Gareth Southgate equally relieved.
England responded to go ahead in the 11th minute with a goal of stunning quality and one which spoke volumes for the brand of football Southgate is trying to establish.
Gareth Southgate gave a start to Marcus Rashford, a player now struggling to make his mark with Manchester United this season. However, the strike was ruled out for a foul on De Gea as Spain hung on to claim three points.
But Shaw's assured return to England duty came to a shuddering halt minutes into second half, with his head appearing to hit Dani Carvajal's hip before bouncing off the turf.
"That balance with the left footer for us, with him and Danny (Rose), was an advantage in several situations".
The hosts did nearly get one back soon after, only for Rashford to be denied by a superb save from David Gea.